CN107556683A - A kind of grid resin and preparation method thereof - Google Patents

A kind of grid resin and preparation method thereof Download PDF

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Publication number
CN107556683A
CN107556683A CN201610513494.2A CN201610513494A CN107556683A CN 107556683 A CN107556683 A CN 107556683A CN 201610513494 A CN201610513494 A CN 201610513494A CN 107556683 A CN107556683 A CN 107556683A
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component
grid
reactor
grid resin
temperature
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许栋
许一栋
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Jiangyin Heng Heng Chemical Co Ltd
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Jiangyin Heng Heng Chemical Co Ltd
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Abstract

A kind of grid resin, including component A, B component and component C, by it is following as mass fraction:Component A:Propane diols 13~14, benzoic acid 1.4~1.6, PET30~33, antioxidant 0.015~0.025;B component:Methyl methacrylate 1.5~2.5, cis-butenedioic anhydride 22~24, vinylacetate 11~12.5, fire retardant 0.015~0.025;Component C:Styrene 12.325~21.055, initiator 0.015~0.025.Not only transparency is high, highly polished, thickening property is good for this kind of resin, simultaneously, it also has stronger inoxidizability, anti-flammability and flexible effect, so as to substantially prolongs the service life of the grid made of this kind of grid, is advantageous to reclaim it and processed.

Description

A kind of grid resin and preparation method thereof
Technical field
The present invention relates to engineering plastics technical field, more particularly to a kind of grid resin and preparation method thereof.
Background technology
Resin flase floor is that one kind glass fibre makees reinforcing material, and unsaturated polyester resin is matrix, by special A kind of board-like material with many spaces being combined is processed, resin flase floor can be used as structural material, may be used as The screen cloth filtered to liquid or powdered substance.Meanwhile in order to avoid liquid or powder and resin during filtering Larger rubbing action occurs for flase floor, so also needing to be lifted the glossiness of resin flase floor, therefore, manufacturing enterprise can be at it PET resin is added in the matrix of unsaturated polyester resin new grid resin is made.Because PET resin molecular structure is highly right Claim, there is certain crystalline orientation ability, so with higher film forming and become second nature, and it has good optical property And weatherability.In addition, PET resin has excellent abrasion performance frictional property and dimensional stability, electrical insulating property and impermeable, matter The features such as light, high in machining efficiency is measured, therefore, it has very big change for the overall performance of grid resin.
However, because resin flase floor is in long-term filter process in reality, also suffer from that material is different degrees of to be rushed The effect of hitting etc., thus, different degrees of bending and deformation will occurs in it, so as to substantially reduce the use of resin flase floor Life-span.
The content of the invention
It is not easy grid resin of deformation and preparation method thereof by force it is an object of the invention to provide a kind of pliability.
The present invention above-mentioned purpose technical scheme is that:
A kind of grid resin, including component A, B component and component C, by it is following according to the mass fraction:
Component A:Propane diols 13~14, benzoic acid 1.4~1.6, PET30~33, antioxidant 0.015~0.025;
B component:Methyl methacrylate 1.5~2.5, cis-butenedioic anhydride 22~24, vinylacetate 11~12.5, fire retardant 0.015~ 0.025;
Component C:Styrene 12.325~21.055, initiator 0.015~0.025.
Preferably, by it is following according to the mass fraction:
Component A:Propane diols 13.6, benzoic acid 1.5, PET31.5, fire retardant 0.02;
B component:Methyl methacrylate 2, cis-butenedioic anhydride 23, vinylacetate 11.7, fire retardant 0.02;
Component C:Styrene 16.64;Initiator 0.02.
Propane diols is good antifreezing agent and plasticizer, so as to its can effectively the freezing tolerance of enhanced grid resin and Pliability, it is avoided at low temperatures by the possibility of bursting by freezing.Also, it is also a kind of lubricant, in processing reaction During can effectively improve the mobile performances of all materials, so as to contribute to material to be sufficiently mixed.
Benzoic acid is a kind of efficient plasticizer, so, it is mixed with grid resin melting can effectively improve lattice The pliability of grid resin.
Methyl methacrylate during reaction can polymerisation generation polymethyl methacrylate, i.e., organic glass Glass.There is transparency height, the characteristic that quality is strong, mechanical strength is big due to rear polymethyl methacrylate is made, so it can The anti-extrusion ability of enhanced grid resin, so as to greatly reduce the possibility of grid resin deformation.
In addition, styrene itself can not only be polymerize, polystyrene is formed, and polystyrene has nontoxic, nothing The characteristic of evil and water white transparency, its light transmittance can reach more than 90%, the printing opacity energy for being advantageous to improve grid resin so as to it Power, and a glass transition temperature is relatively high, so also reducing the deformation possibility of resin flase floor to a certain extent.
Secondly, cis-butenedioic anhydride and styrene can also carry out a certain degree of polymerisation generation SAM resins in kettle is diluted, its With excellent mechanics and electric property and high-temperature stability, so as to further increase the high temperature resistant for improving grid resin And the ability of the anti-deformation of resistance to compression.
Preferably, the antioxidant in component A is 3,5- di-tert-butyl-4-hydroxybenzoic acids and its derivative.
3,5- di-t-butyl -4-4- hydroxybenzoic acids, are not only a kind of antioxidant, improve the ageing-resistant of grid resin Ability, the service life of product made of grid resin can be extended.Meanwhile contain 3,5- di-t-butyl -4-4- hydroxy benzenes knots The compound of structure also has anti-inflammatory, antiviral and antineoplastic action, thus, material filtering of this kind of grid resin to foodstuff After crossing, food will carry part 3,5- di-t-butyl -4-4- hydroxybenzoic acids, so as to user in certain degree Health also have very big beneficial effect.
Preferably, the fire retardant in B component is nitrogenated flame retardant.
Preferably, the nitrogenated flame retardant is the mixture of melamine and pentaerythrite.
Nitrogen combustion inhibitor is added in grid resin, and this kind of nitrogen combustion inhibitor is the mixture of melamine and pentaerythrite, Due to melamine when being thermally decomposed it is caused be CO2, N2 and NH2 without producing halide, therefore be environment friend The fire retardant of good property, meanwhile, and pentaerythrite mixes the heat endurance that can improve melamine with melamine, so as to significantly With improving grid resin flame retardant effect.
Furthermore pentaerythrite is also a kind of efficiently plasticizer, so as to which it is also beneficial to the pliability of raising grid resin, And then be advantageous to improve the pliability of whole grid resin, reduce the possibility of its compression deformation.
Preferably, the initiator of component C is AIBN.
AIBN is efficient initiator, and dissociative reaction can easily occur for its molecule, forms very high point of activation energy Son, so as to promote each polymerized monomer to carry out rapidly polymerisation, so as to substantially increase the preparation efficiency of whole grid resin.
A kind of preparation method of grid resin, comprises the following steps:
S1, the component C for weighing by mass fraction requirement respective quality are put into dilution kettle, and ensure that temperature is normal temperature state, Crawl opens stirring, until stirring;
S2, weigh corresponding B component by mass fraction requirement and put into reactor, start to warm up to 120-140 DEG C, and be incubated anti- Answer 3~4 hours;
S3, after the completion for the treatment of S2, control and evaporate 100-105 DEG C of a temperature, treat that temperature of charge rises to 215 DEG C;
S4, the temperature for keeping S3, question response to acid number drop to below 3mKOH/g, reactor are carried out to be cooled to 190 DEG C of processing;
S5, after the completion for the treatment of S4 cooling, the component A that respective quality is weighed by mass fraction requirement is put into reactor, heating To 203-206 DEG C:
S6, treat that the material acid number of reactor in S5 is less than 43mKOH/g, Cone & Plate viscosity is carried out at 1.95~2.05 (125 DEG C) Vacuumize reaction;
S7, the material acid number of reactor in S6 is treated to 22~26mKOH/g, Cone & Plate viscosity is carried out between 4.5~5 (125 DEG C) Cooling, and resulting material is transferred in S1 dilution kettle and is stirred dilution;
S8, discharge manufactured finished product grid resin in S7 barrelling, and is packed.
Preferably, it is necessary to be passed through nitrogen to reactor during S3 reacts, nitrogen flow is controlled in 6~10m/ h。
Preferably, it is necessary to which nitrogen flow is increased into 20~30m in S4 course of reaction3/h。
Preferably, in S6 dilution, dilution temperature is less than or equal to 75 DEG C.
In summary, the invention has the advantages that:
1. by the use of propane diols and benzoic acid as plasticizer, the pliability of grid resin is improved, so as to make it after deformation It is rapid to recover;
2. because methyl methacrylate generates polymethyl methacrylate after polymerisation, it not only has good transparency, Its mechanics ability also compares strong simultaneously, so improving the possibility of grid resin compression deformation;
3. being also added into antioxidant, fire retardant and initiator in grid resin, therefore, which also enhances itself corresponding item Energy.
Embodiment
Embodiment one,
Weigh styrene 123.25kg and AIBN0.15kg to put into dilution kettle, keep the temperature at normal temperature state, crawl is opened Stirring is opened, is directly well mixed mixture;Afterwards, methyl methacrylate 15kg, cis-butenedioic anhydride 220kg, vinylacetate are weighed 110kg, melamine 0.09kg and pentaerythrite 0.06kg are put into reactor, are started to warm up to 120-140 DEG C, and be incubated Reaction 3~4 hours;Then, nitrogen is passed through to reactor, nitrogen flow control evaporates a temperature 100-105 in 6~10m/h, control DEG C, treat that temperature of charge rises to 215 DEG C;Increase nitrogen flow to 20~30m/h, question response to acid number drops to below 3mKOH/g, will Reactor carries out being cooled to 190 DEG C of processing;Weigh propane diols 130kg, benzoic acid 14kg, PET30kg and 3,5- di-t-butyl -4- Hydroxybenzoic acid 0.15kg is put into reactor, and is warming up to 203-206 DEG C;The material acid number of question response kettle is less than 43mKOH/g, Cone & Plate viscosity carry out vacuumizing reaction at 1.95~2.05 (125 DEG C);The material acid number of question response kettle is to 22 ~26mKOH/g, Cone & Plate viscosity are cooled to 75 DEG C, material are transferred to equipped with the dilute of styrene between 4.5~5 (125 DEG C) Release in kettle and be diluted;By the discharging barrelling of manufactured finished product grid resin, and packed.
Embodiment two,
Weigh styrene 210.55kg and AIBN0.25kg to put into dilution kettle, keep the temperature at normal temperature state, crawl is opened Stirring is opened, is directly well mixed mixture;Afterwards, methyl methacrylate 25kg, cis-butenedioic anhydride 240kg, vinylacetate are weighed 125kg, melamine 0.15kg and pentaerythrite 0.1kg are put into reactor, are started to warm up to 120-140 DEG C, and be incubated Reaction 3~4 hours;Then, nitrogen is passed through to reactor, nitrogen flow is controlled in 6~10m3/ h, control evaporate a temperature 100- 105 DEG C, treat that temperature of charge rises to 215 DEG C;Increase nitrogen flow to 20~30m3/ h, question response to acid number drop to 3mKOH/g with Under, reactor is carried out to be cooled to 190 DEG C of processing;Weigh propane diols 140kg, benzoic acid 16kg, PET330kg and the uncle of 3,5- bis- Butyl -4-HBA 0.25kg puts into reactor, and is warming up to 203-206 DEG C;The material acid number of question response kettle is low In 43mKOH/g, Cone & Plate viscosity carries out vacuumizing reaction at 1.95~2.05 (125 DEG C);The material acid number of question response kettle is extremely 22~26mKOH/g, Cone & Plate viscosity are cooled to 75 DEG C, material are transferred to equipped with styrene between 4.5~5 (125 DEG C) It is diluted in dilution kettle;By the discharging barrelling of manufactured finished product grid resin, and packed.
Embodiment three,
Weigh styrene 166.4kg and AIBN0.2kg to put into dilution kettle, keep the temperature at normal temperature state, crawl is opened Mixture, is directly well mixed by stirring;Afterwards, methyl methacrylate 20kg, cis-butenedioic anhydride 230kg, vinylacetate are weighed 117kg, melamine 0.12kg and pentaerythrite 0.08kg are put into reactor, are started to warm up to 120-140 DEG C, and be incubated Reaction 3~4 hours;Then, nitrogen is passed through to reactor, nitrogen flow is controlled in 6~10m3/ h, control evaporate a temperature 100- 105 DEG C, treat that temperature of charge rises to 215 DEG C;Increase nitrogen flow to 20~30m3/ h, question response to acid number drop to 3mKOH/g with Under, reactor is carried out to be cooled to 190 DEG C of processing;Weigh propane diols 136kg, benzoic acid 15kg, PET315kg and the uncle of 3,5- bis- Butyl -4-HBA 0.2kg puts into reactor, and is warming up to 203-206 DEG C;The material acid number of question response kettle is less than 43mKOH/g, Cone & Plate viscosity carry out vacuumizing reaction at 1.95~2.05 (125 DEG C);The material acid number of question response kettle is to 22 ~26mKOH/g, Cone & Plate viscosity are cooled to 75 DEG C, material are transferred to equipped with the dilute of styrene between 4.5~5 (125 DEG C) Release in kettle and be diluted;Add the discharging barrelling of manufactured finished product grid resin, and packed.
Example IV,
Weigh styrene 166.4kg and AIBN0.15kg to put into dilution kettle, keep the temperature at normal temperature state, crawl is opened Mixture, is directly well mixed by stirring;Afterwards, methyl methacrylate 20kg, cis-butenedioic anhydride 220kg, vinylacetate are weighed 125kg, melamine 0.12kg and pentaerythrite 0.08kg are put into reactor, are started to warm up to 120-140 DEG C, and be incubated Reaction 3~4 hours;Then, nitrogen is passed through to reactor, nitrogen flow is controlled in 6~10m3/ h, control evaporate a temperature 100- 105 DEG C, treat that temperature of charge rises to 215 DEG C;Increase nitrogen flow to 20~30m3/ h, question response to acid number drop to 3mKOH/g with Under, reactor is carried out to be cooled to 190 DEG C of processing;Weigh propane diols 130kg, benzoic acid 16kg, PET330kg and the uncle of 3,5- bis- Butyl -4-HBA 0.2kg puts into reactor, and is warming up to 203-206 DEG C;The material acid number of question response kettle is less than 43mKOH/g, Cone & Plate viscosity carry out vacuumizing reaction at 1.95~2.05 (125 DEG C);The material acid number of question response kettle is to 22 ~26mKOH/g, Cone & Plate viscosity are cooled to 75 DEG C, material are transferred to equipped with the dilute of styrene between 4.5~5 (125 DEG C) Release in kettle and be diluted;By the discharging barrelling of manufactured finished product grid resin, and packed.
Comparative example one,
Weigh styrene 166.4kg and AIBN0.15kg to put into dilution kettle, keep the temperature at normal temperature state, crawl is opened Mixture, is directly well mixed by stirring;Afterwards, methyl methacrylate 20kg, vinylacetate 125kg, melamine are weighed Amine 0.12kg and pentaerythrite 0.08kg are put into reactor, are started to warm up to 120-140 DEG C, and insulation reaction 3~4 is small When;Then, nitrogen is passed through to reactor, nitrogen flow is controlled in 6~10m3/ h, control evaporate 100-105 DEG C of a temperature, treat material Temperature rises to 215 DEG C;Increase nitrogen flow to 20~30m3/ h, question response to acid number drop to below 3mKOH/g, reactor are entered Row is cooled to 190 DEG C of processing;Weigh propane diols 130kg, benzoic acid 16kg, PET330kg and 3,5- di-t-butyl -4- hydroxy benzenes Formic acid 0.2kg is put into reactor, and is warming up to 203-206 DEG C;The material acid number of question response kettle is less than 43mKOH/g, cone-plate Viscosity carries out vacuumizing reaction at 1.95~2.05 (125 DEG C);The material acid number of question response kettle is bored to 22~26mKOH/g Plate viscosity is cooled to 75 DEG C between 4.5~5 (125 DEG C), material is transferred in the dilution kettle equipped with styrene carry out it is dilute Release;By the discharging barrelling of manufactured finished product grid resin, and packed.
Comparative example two,
Weigh methyl methacrylate 20kg, cis-butenedioic anhydride 230kg, vinylacetate 117kg, melamine 0.12kg, pentaerythrite 0.08kg and AIBN0.2kg are put into reactor, are started to warm up to 120-140 DEG C, and insulation reaction 3~4 hours;Then, Nitrogen is passed through to reactor, nitrogen flow is controlled in 6~10m3/ h, control evaporate 100-105 DEG C of a temperature, treat that temperature of charge rises to 215℃;Increase nitrogen flow to 20~30m3/ h, question response to acid number drop to below 3mKOH/g, reactor are cooled to 190 DEG C of processing;Weigh propane diols 136kg, benzoic acid 15kg, PET315kg and 3,5- di-tert-butyl-4-hydroxybenzoic acid 0.2kg Put into reactor, and be warming up to 203-206 DEG C;The material acid number of question response kettle is less than 43mKOH/g, and Cone & Plate viscosity exists When 1.95~2.05 (125 DEG C), carry out vacuumizing reaction;The material acid number of question response kettle is to 22~26mKOH/g, Cone & Plate viscosity Between 4.5~5 (125 DEG C), it is cooled to 75 DEG C and is diluted;By the discharging barrelling of manufactured finished product grid resin, and wrapped Dress.
By embodiment one to example IV and the properties of comparative example one and comparative example two, data below is obtained Table:
The bending bullet of grid resin when the copolymer when no styrene and cis-butenedioic anhydride is can be seen that by above-mentioned test data Property modulus and bending strength have very big decline, and then pliability is just greatly reduced, meanwhile, without styrene from figure Into polymer, the light transmittance of whole grid resin also reduced, the grid resin participated in without cis-butenedioic anhydride, its pliability than There is no the more of the grid resin decline of styrene.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art Member can make the modification of no creative contribution to the present embodiment as needed after this specification is read, but as long as at this All protected in the right of invention by Patent Law.

Claims (10)

1. a kind of grid resin, including component A, B component and component C, it is characterised in that:
By it is following according to the mass fraction:
Component A:
B component:
Component C:
Styrene 12.325~21.055
Initiator 0.015~0.025.
A kind of 2. grid resin according to claim 1, it is characterised in that:
By below by according to the mass fraction:
Component A:
B component:
Component C:
Styrene 16.64
Initiator 0.02.
A kind of 3. grid resin according to claim 1 or 2, it is characterised in that:Antioxidant in component A is the uncles of 3,5- bis- Butyl -4-HBA or and its derivative.
A kind of 4. grid resin according to claim 1 or 2, it is characterised in that:Fire retardant in B component is fire-retardant for nitrogen system Agent.
A kind of 5. grid resin according to claim 4, it is characterised in that:The nitrogenated flame retardant is melamine and season The mixture of penta tetrol.
A kind of 6. grid resin according to claim 1 or 2, it is characterised in that:The initiator of component C is AIBN.
7. a kind of preparation method of grid resin as described in any one claim in claim 1 or 2, including following step Suddenly:
S1, the component C for weighing by mass fraction requirement respective quality are put into dilution kettle, and ensure that temperature is normal temperature state, Crawl opens stirring, until stirring;
S2, weigh corresponding B component by mass fraction requirement and put into reactor, start to warm up to 120-140 DEG C, and be incubated anti- Answer 3~4 hours;
S3, after the completion for the treatment of S2, control and evaporate 100-105 DEG C of a temperature, treat that temperature of charge rises to 215 DEG C;
S4, the temperature for keeping S3, question response to acid number drop to below 3mKOH/g, reactor are carried out to be cooled to 190 DEG C of processing;
S5, after the completion for the treatment of S4 cooling, the component A that respective quality is weighed by mass fraction requirement is put into reactor, heating To 203-206 DEG C;
S6, treat that the material acid number of reactor in S5 is less than 43mKOH/g, Cone & Plate viscosity is carried out at 1.95~2.05 (125 DEG C) Vacuumize reaction;
S7, the material acid number of reactor in S6 is treated to 22~26mKOH/g, Cone & Plate viscosity is carried out between 4.5~5 (125 DEG C) Cooling, and resulting material is transferred in S1 dilution kettle and is stirred dilution;
S8, discharge manufactured finished product grid resin in S7 barrelling, and is packed.
A kind of 8. preparation method of grid resin according to claim 7, it is characterised in that:During S3 reacts, Need to be passed through nitrogen to reactor, nitrogen flow is controlled in 6~10m/h.
A kind of 9. preparation method of grid resin according to claim 8, it is characterised in that:In S4 course of reaction, Need nitrogen flow increasing to 20~30m/h.
A kind of 10. preparation method of grid resin according to claim 9, it is characterised in that:It is dilute in S6 dilution Temperature is released less than or equal to 75 DEG C.
CN201610513494.2A 2016-06-30 2016-06-30 A kind of grid resin and preparation method thereof Pending CN107556683A (en)

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CN101555315A (en) * 2009-05-18 2009-10-14 上海新天和树脂有限公司 Modified unsaturated polyester resin of polyethylene glycol, preparation method and application of glass steel grating
CN105482087A (en) * 2015-12-28 2016-04-13 肇庆福田化学工业有限公司 Anti-yellowing unsaturated polyester resin and synthetic method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN101531763A (en) * 2009-04-02 2009-09-16 上海交通大学 Method for preparing toughened unsaturated polyester glass fibre composite material
CN101555315A (en) * 2009-05-18 2009-10-14 上海新天和树脂有限公司 Modified unsaturated polyester resin of polyethylene glycol, preparation method and application of glass steel grating
CN105482087A (en) * 2015-12-28 2016-04-13 肇庆福田化学工业有限公司 Anti-yellowing unsaturated polyester resin and synthetic method thereof

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Application publication date: 20180109